Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
  • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
  • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
  • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
  • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
  • C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
  • C08G65/3342—Polymers modified by chemical after-treatment with organic compounds containing sulfur having sulfur bound to carbon and hydrogen
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones

Definitions

• This invention relates to polyfunctional crosslinkable compounds and in particular to such prepolymers and polymers having polyoxyalkylene chains.
• a number of resins have been proposed for use on wool or other keratinous fibres to confer desirable properties such as shrink-resistance, or shape stabilization.
• resins are polymers based on a triol residue having polyoxypropylene side chains terminated with radicals containing thiol or isocyanate groups.
• Prepolymers of this kind can be applied to wool and cured by chain extension and cross linking to provide shrink resistance and permanent press properties.
• crosslinkable moieties examples include isocyanate groups (blocked or unblocked), thiol groups, thiosulphate (Bunte salt) groups or an activated double bond.
• Thiol groups are preferably attached to respective carboxylic acid residues.
• Particularly preferred compounds of the invention are water soluble and contain one or more solubilizing groups such as --SSO 3 - or --NHCO SO 3 - .
• water solubility may be achieved by the inclusion in the molecule of one or more --COO -M + groups wherein M - is an alkali metal, ammonia, amine or quaternary ammonium cation.
• the invention further includes an aqueous solution of such a water soluble compound.
• polycarboxylic acids as used in the present specification is intended to include dicarboxylic acids as well as acids containing three or more carboxyl groups.
• One group of compounds of the invention has the general formula:
• R is preferably a trivalent residue.
• R may be ##STR1##
• X may be omitted, but if present is preferably --OOC--(CH 2 ) 4 --, --OOC--(CH 2 ) 2 --, --OOC--OH 2 --, --OOC--(CH 2 ) 8 --, --OOC--CH ⁇ CH-- or --OOC--CH 2 --C(CH 2 )--.
• the crosslinking moiety in the terminal group Y may be, for example, a thiol group, a Bunte salt group, an isocyanate group (blocked or unblocked), or an activated double bond.
• Y may therefore be such as: --CO--NH--R--NCO where R is, for example, hexamethylene, diphenyl methane or toluylene; --OC--CH ⁇ CH--COOR where R is an aliphatic group, --OC--R--SH where R is an alkylene group, preferably methylene; or --OC--CH 2 --SSO 3 - .
• the compounds of the invention may be prepared in a number of ways.
• difunctional resins are not so effective as polymers of higher functionality.
• straight-chain diols may be linked in such a way as to increase the functionality of the molecule. They can undergo both acid and base-catalysed esterification reactions, and the preferred route to a triol is half-esterification with citric acid, a cheap, readily available tribasic acid.
• This is followed by a second step, in which the crosslinkable groups are introduced, and where this can be achieved by esterification, it can be carried out immediately after the first step, in the same reaction mixture.
• the intermediate citrate ester may be isolated before proceeding.
• Poly(tetramethylene oxide) diols can be made from tetrahydrofuran (T.H.F.) and are available under the trade name ⁇ Polymeg ⁇ (Quaker Oats). Such diols have the structure:
• Thiol groups may be introduced, for example, by capping with thioglycollic, as in the following typical reaction sequence: ##STR3##
• mercapto acids than thioglycollic acid may be used, for example thiomalic acid.
• thiomalic acid When a monomercaptodicarboxylic acid such as thiomalic acid is used, the compound is soluble in aqueous alkali, forming a salt.
• polybasic aliphatic acids may be used, for example tricarballylic, aconitic, isocitric and hydroxycitric acids, but citric acid is preferred as it is cheap and readily available.
• Bunte salt groups may, for example, be introduced by capping with chloroacetic acid followed by treatment with Na 2 S 2 O 3 .
• the following is a typical reaction sequence: ##STR4##
• R in the general formula I, is ##STR5## X is omitted, n is 13 or 14, M is 4, p is 3, and Y is --CO--NH--(CH 2 ) 6 --NCO in the case of formula III, --OC--CH 2 --SH in the case of formula IV, or --OC--CH 2 --SSO.sub. 3 - Na + in the case of formula V.
• a polyhydric alcohol may be esterified with a single-equivalent excess of a poly-basic, e.g. dibasic, acid to yield the corresponding polybasic ester, which may be subsequently esterified with a diol, followed by attachment of reactive groups.
• a poly-basic e.g. dibasic
• H.M.D.I. may be replaced by 3 moles of monochloroacetic acetic, and the chlorester further reacted with sodium thiosulphate to produce a Bunte salt prepolymer.
• Any polyhydroxy compound may be used in this process but the following are particularly successful: glycerol, trimethylolpropane, pentaerythritol, hexane-- 1,2,6 -- triol, tris (hydroxymethyl) methylamine and triethanolamine.
• Any polybasic acid may be used but dibasic acids such as malonic, succinic, adipic, sebacic, and itaconic acids are preferred, and sebacic and adipic acids are particularly useful.
• Tribasic acids e.g. citric acid, can also be used.
• the polymers of formula VIII may be prepared by esterifing a straight-chain diol with a dibasic acid which contains a pendant reactive groupm such as glutamic or malic acid. In this process, the functionality of the product depends upon the ratio of the reactants.
• the reaction can be represented as ##STR10## where Z is a reactive group such as --OH, --NH 2 or --SH. The group is then further reacted. For example if glutamic acid is used, Z is NH 2 : ##STR11##
• the pendant --OH group is reacted to introduce the cross-linking reactive group, or if mercapto succinic acid is used the -SH group reacts with, e.g. a di-isocyanate.
• the terminal carboxyl groups would also react with the di-isocyanate unless capped, e.g. esterified.
• a one mole excess of the diol may be used. In this latter case a hydroxy terminated polymer results, and if x is 2, the product is trifunctional, if x is 3, tetrafunctional and so on.
• x is from 2 to 5.
• products of this type may be further capped on the terminal carboxyl or hydroxy groups.
• the reaction can be represented as ##STR13## e.g. 4 moles of mercaptosuccinic + 3 moles of Polymeg 1000 yields a tetrafunctional thiol resin of molecular weight about 3400 terminated with COOH groups.
• hydroxy-terminated polymers may be prepared by reversing the ratio of reactants used. Products of these types may be further capped via their terminal carboxyl or hydroxy groups if desired.
• thiol-terminated polymers previously available have in general been insoluble in water.
• thiol (mercapto) groups may be introduced by, for example, esterification with mercaptocarboxylic acid, such as mercaptopropionic or thioglycollic acid.
• alkene groups formed, for example as the half-esters of unsaturated dibasic acids or their anhydrides, e.g. ##STR14##
• Epoxy-terminated isocyanates formed by the addition of e.g. glycidol to the isocyanates of (ii) above.
• All the compounds of the invention exhibit superior light fastness, when used in textile applications, than comparable resins previously available. While the usefulness of the invention in no way depends on the correctness or otherwise of the supposition, we believe that using, in polymers polyoxyalkylene chains which have side branches, e.g. ##STR16## renders such polymers more liable to degradation owing to splitting of the branched oxyalkylene chain by light energy. Such degradation leads to a lessening of the shrink-resist or permanent press effect, and may in the case of thiol resins give rise to unpleasant smells.
• the unbranched polyoxyalkylene chains used in all the compounds of the present invention are, we have found, far more stable to light when cured and are therefore more suitable for use in textile finishing operations where the textiles, e.g. garments, are subsequently going to be exposed to light.
• curable thiol prepolymers have been insoluble in water at pH values low enough not to affect a keratinous substrate. Thus they had to be applied to textiles from solvent, which is costly as it requires recycling of the solvent and expensive machinery, or from aqueous emulsions. Application from aqueous emulsions can suffer from the defect of inadequate spreading of the polymer on the fibre surface. Where catalysts are used, these are generally dissolved in the aqueous phase and can cause inadequate curing of the interior of the droplets of emulsified resin leading to the deposition of ⁇ capsules ⁇ of uncured resin rather than the even, fully cured film required in textile finishing.
• the preferred water-soluble thiol compounds of the invention are free from these defects.
• the thiol compounds of the invention exhibit superior light fastness, when used in textile applications, than thiol resins previously available.
• the invention further includes a process for finishing keratinous fibres which comprises treating the fibres with a compound according to the invention and curing the compound, or allowing it to cure, on the fibres.
• the invention also includes a process for the simultaneous dyeing and shrink-resist treatment of keratin fibres which comprises impregnating the fibres at a pH of 2- 10, preferably e.g. 3- 6, and at a temperature of 10° - 60° C. with an aqueous composition comprising
• Isocyanate compounds according to the invention for use in this simultaneous dyeing and deposition procedure should be blocked or at least slow reacting with water and should be soluble (e.g. the bisulphite adduct) or emulsifiable (e.g. the imine adduct).
• Bunte salt compounds of the invention are water-soluble and fully compatible with dyeing.
• Thiol polymers of this invention can be used provided care is taken to select a dye that does not react with the thiol groups of the polymer.
• the dye and the cross-linkable compound are preferably applied to the fibres by means of a pad mangle.
• the viscosity of the liquor is preferably adjusted to a value in the range of 5- 20 poise measured at a low rate of shear. (Pad liquors normally employed exhibit non-Newtonian viscosity characteristics and the measured viscosity characteristics depend on the applied shear forces).
• the viscosity should be below 20 poise so that the liquor is sufficiently fluid and should be above 5 poise to prevent gross migration of the liquor through the stored dyed material and to prevent pressure marking and stitch marking which are faults which can become apparent during storage.
• the liquor can be adjusted to the required value using a thickener and concentrations in the range 10-30 g/l are normally suitable.
• Thickeners which can be employed are based, for example, on carboxymethyl cellulose, locust bean gum, Guar gum and the like.
• the preferred thickener, which imparts thixotropic properties to the pad liquor, is that sold under the trade name Guaranate AP5.
• the keratin fibres to be treated will normally be the wool of sheep, but may if desired be derived from alpaca, cashmere, mohair, vicuna, guanaco, camel hair or llama or blends of these materials with sheep's wool.
• the fibrous materials may consist wholly of wool or be a blend of wool with synthetic fibrous and filamentary material or with natural or regenerated cellulosic fibres. In general, however, the material should contain at least 30% wool and the invention is especially appropriate to the treatment of 100% wool-containing material.
• the wool may be treated at any stage during textile processing and may be in the form of tops, card sliver, noils, yarns, threads, woven or knitted fabrics, non-woven fabrics, pile fabrics or made-up garments.
• the dyes which can be employed in the present process are water soluble and contain anionic solubilising groups.
• acid levelling, acid milling, premetallised and solubilised vat dyes can be used but especially good results can be obtained with fibre-reactive dyes, i.e. dyes which can react with the keratin fibres and become chemically bonded thereto.
• the acid levelling dyestuffs can be, for example, of the azo type and should be water soluble and contain at least one anionic solubilising group, generally a sulphonic acid group.
• Acid milling dyes generally have a greater molecular weight and fewer solubilising groups than the acid levelling dyes, but there is no rigid distinction between the two classes.
• the premetallised dyes comprise a class of dyes having o,o - dihydroxy azo, o-amino- o-hydroxy azo or o-carboxyl- o-hydroxy azo groups which are co-ordinated to a metal atom, for example chromium or cobalt.
• the dyes may be used as 1:1 or 2:1 complexes.
• Vat dyes which are most commonly of the indigoid or anthraquinone structure, are solubilised by conversion to their water-soluble leuco esters and can subsequently be developed after application, by oxidation to the insoluble form.
• the reactive dyes which are of especial interest, can include the following groups: epoxy-, ethyleneimino-, isocyanate-, isothiocyanate-, carbamic acid aryl ester-, propiolic acid amido-, monochloro-, and dichlorocrotonylamino-chloroacrylamino-, acrylamino, sulphohalo-, sulphuric acid ester, sulphoxy, labile halogen atoms, trichloropyridazino-, dichloroquinoxalino-, allylsulphonyl-, thiosulphate, and certain reactive ammonium of hydroxonium residues, monochlorodifluoropyrimidine, carboxymethylcarbodithionate.
• highly reactive dyes for example those incorporating a 2,4-dichlorotriazinyl-, monochlorodifluoropyrimidine, vinylsulphonyl-, 2,3-dichloroquinoxalino-, or bromo-acrylamido group.
• less reactive halogen-containing dyes they may be rendered more reactive by applying them in admixture with a tertiary amine, for example triethylamine.
• the term "reactive dye” as used herein also includes whitening agents which react with the fibre in the same way.
• the additives of general formula IX are normally present in concentrations of 25-300 grams per liter. Urea, thiourea and sulphamide may be employed.
• the incorporation of such reducing agents may be desirable in the case of fabrics where the dyeing is liable to be skittery or unlevel.
• the amount of reducing agent per 100 parts by weight of liquor may, for example, be from 1 to 50, preferably from 1 to 20 parts by weight.
• the use of sodium bisulphite, which is preferred, has the advantage that it exerts a bleaching action on the wool and therefore allows very bright shades to be obtained.
• not all reducing agents are equally effective with a particular dye, and the particular reducing agent or agents to be used with a given dye to obtain the optimum results should be ascertained by routine trial.
• the water-soluble cross-linkable compounds according to the invention often exhibit surface active properties.
• surfactant can if desired be added to the liquor and suitable surfactants include non-ionic condensation products of nonylphenols with ethylene oxide, e.g. polyoxyethylated nonyl phenols containing 10-30 mols of ethylene oxide and anionic sulpho-succinate derivatives.
• a suitable non-ionic surfactant is, for example, sold under the Trade Mark Lissapol N.
• non-ionic acid amide-derived surfactants may be used, for example a condensation product of coconut oil fatty acids with diethanolamine such as that available under the trade name Atexal PN-VP.
• the impervious sheet material may be a film of hydrophobic material, e.g. a film of hydrophobic plastics material such as polyethylene. Polyvinyl acetate film or printers paper may also be employed. After the storage period the goods are washed to remove excess or unfixed dye.
• reducing agents or bases can be employed in the form of aqueous solutions which contain preferably 0.1 to 2.0% by weight of the dissolved material based on the weight of the solution.
• Ammonia is the preferred agent to use in the after-treatment step.
• This treatment with a solution of a reducing agent or base may be, for example, for a period of 15 minutes at a temperature from ambient temperature to 100° C. generally about 60° C.
• the reaction mixture was cooled, washed several times with water to remove excess acid, dried with magnesium sulphate, and then solvent and other low molecular weight impurities removed under reduced pressure.
• the yield of pale straw-coloured polymer was 269 grams (95% of theory).
• the mixture was heated at 100° C. for 1 hour and then at 110° C. for 1/2 an hour, after which it was allowed to cool at room temperature. A 1 ml aliquot of the mixture dissolved completely in 50 ml of water.
• the reaction mixture was diluted with water, made 2% with respect to sodium sulphite, padded onto wool fabric, dried at 100° C. for 15 minutes, given a brief wash off and dried again at 100° C. for 5 minutes.
• the finished fabric was then tested for machine washability as described and the area shrinkage results are shown in Table 1 and the differential shrinkage due to exposure to light in Table 2.
• glycol was reacted with citric acid in 3:1 molar ratio followed by esterification with chloroacetic acid and then replacement of the chlorine atom with --SSO 3 groups, as in Example 1.
• Wool fabrics were impregnated on a pad mangle with the following composition:
• the impregnated material was wound onto a former, covered with a polyethylene sheet and stored for 24 hours.
• the material was then washed with 1% aqueous ammonia at a liquor ratio of 15:1 for 15 minutes and dried for 15 minutes at 60° to 70° C.
• H.M.D.I. and 250 ml A. R. toluene were stirred under nitrogen in a vessel equipped with a reflux condenser and dropping funnel. From the latter, 100 grams (0.0313 mole) of Polymer IV dissolved in 100 ml A.R. toluene was added slowly over a period of 15 minutes, and then the temperature of the mixture was gradually raised to reflux over another 15 minutes. After an hour at this temperature (approximately 116° C.), the mixture was allowed to cool, and excess H.M.D.I. and solvent were removed under reduced pressure.
• Full-decatising (high temperature steam flat-setting) was carried out between cotton wrappers in a vacuum autoclave using 15 lb/in 2 gauge steam pressure for 5 min.
• the bromo analogue of Polymer I was prepared employing the conditions of Example 1 but substituting bromoacetic acid for chloroacetic acid.
• the thiosulphato derivative was prepared by reacting the bromo analogue with sodium thiosulphate, according to the method described in Example 1 except that isopropanol is used as a solvent in place of DMF. Its application to wool fabric was identical to that described for Polymer II. The test results are shown in Table 5.
• Polymer VI 25 grams (0.02027 g. equivalents) Polymer VI were dissolved in 30 ml toluene, and added to this were 1.5 grams (0.02027 mole) glycidol, 1 drop of dibutyltin dilaurate and 50 mg. triethylenediamine. The mixture was held for 2 hours at room temperature, after which time an infra-red spectrum of the product showed no peak at 2265 mm, indicating that all isocyanate groups were blocked.
• the solution was diluted with perchloroethylene and padded onto woollen doctor flannel. It was then dried, cured by authclaving for 5 mins. at 15 p.s.i., and washed.
• the bisulphite-adduct of Polymer XII was prepared by the method described in Example 10.
• the resulting pale polymer was padded onto woollen doctor flannel from aqueous solution, dried at 80° for 10 minutes, cured by autoclaving for 5 minutes, and given a machine wash (see Example 4).
• Example 8 The method of Example 8 was followed to prepare the glycidol-blocked version of Polymer XII, using:
• Example 9 The method of Example 9 was followed to prepare the aziridine-terminated version of Polymer XII, using:
• the polymer was applied from solvent, and cured by drying and steaming (5 mins). The test results are shown in Table 13.
• This poly(hexamethylene oxide) was then esterified with citric acid, in the manner previously described (see Example 4), and subsequently capped with hexamethylene diisocyanate as for Polymer V.
• Wool fabrics were impregnated on a pad mangle with the following composition per liter:
• the impregnated material was wound onto a former, covered with a polyethylene sheet and stored for 24 hours. Then either a 1% sulphuric acid, hydrogen peroxide or sodium carbonate solution, preferably containing a heavy metal salt, was padded on to the wet stored fabric and allowed to remain for 15 minutes to effect curing of the polymer or, alternatively, the fabric was placed in a bath of the acid, oxidising agent or base for 15 minutes. The material was then washed with 1% aqueous ammonia at a liquor ratio of 15:1 for 15 minutes and dried for 15 minutes at 60°-70° C.
• cross-linkable compound used in this Example can be replaced by other water-soluble or emulsifiable compounds of the invention and satisfactory results obtained.
• Other dyes can be substituted for Procion Red MG.
• the polymer was applied to wool fabric by padding from solution in 50% aqueous isopropanol, the solution also containing 2% sodium metabisulphite.
• the fabric was dried at 120° C. for 10 minutes, then rinsed to remove salts.
• Tables 20 and 21 show the results of further shrinkage and smooth drying tests on fabrics treated with polymers according to this invention.
• the following examples relate to polymers with terminal cross-linkable thiol groups.
• the fabrics used were worsted serge of 13/14 oz per running yard (270 g/m 2 ) and "doctor" flannel (plain weave woollen fabric 185 g/m 2 ).
• the fabric After being padded, the fabric was dried at 100° C. for 15 minutes in a forced-air oven, and then left at room temperature overnight. The alkali and surfactant were then removed by giving the fabric three 15-minute washes in water in a laboratory dolly-washer. The process was completed by allowing the fabric to dry in air at room temperature, followed by full-decatising (high temperatures steam flat-setting) between cotton wrappers in a vacuum autoclave using 15 lb/in 2 gauge steam pressure for 5 min.
• Example 1 The application of the polymers to wool from aqueous emulsions (3% KHCO 3 ) was as described in Example 1.
• the results from tests on the treated fabrics are given in Tables 24 and 25.
• the results of different washing tests in Table 25 were obtained with fabrics treated with emulsions containing 2% KHCO 3 . Except where otherwise indicated washing was for 3 hours in 15 liters (Cubex machine).
• the polymer was applied to wool fabric from a 2% sodium carbonate solution and was cured by drying at 120° C. for 10 minutes. The remainder of the fabric finishing process as described in Example 20.
• the results of shrinkage tests are shown in Table 26, the wash test being conducted in 15 liters of pH 7 buffer (Cubex machine).
• Example 20 The reaction mixture was worked up by the method described in Example 20, the yield of colourless polymer being 93% of theory.
• Polymer XXIX was emulsified and applied as in Example 20, and the treated wool fabric was evaluated for shrink-resistance and smooth drying index. The results are in Table 27.
• Polymer XXX was the same as that of Polymer XXIX, except that 21.64 grams (0.1481 mole) adipic acid replaced the sebacic acid.
• the application of the polymer to wool fabric was from aqueous emulsion (containing 3% KHCO 3 ) and the results of fabric performance are in Table 28.
• the reaction mixture was worked up in the usual way (see Example 1), and the yield of pale yellow polymer was 162 g.
• the polymer was applied to wool fabric from an aqueous emulsion containing (3% KHCO 3 ) and the results of wash tests are in Table 29.
• Example 23 The method described in Example 23 was followed, using as reactants in the first stage 6.62 grams (0.0494 mole) tris(hydroxymethyl)propane and 21.64 grams (0.1481 mole) adipic acid. All reaction stages went to completion, and the yield of colourless polymer was 95% of theory.
• the polymer was applied to wool fabric from aqueous emulsion (containing 3% KHCO 3 ) and the curing and testing was as described in Example 20. The results are in Table 30.
• Example 23 The procedure in Example 23 was followed, using as first stage reactants, 6.62 grams (0.0494 mole) tris(hydroxymethyl)propane and 30 grams (0.1483 mole) sebacic acid. The predicted volumes of water were collected at each stage, and the yield of colourless polymer was 97% of theory.
• the polymer was applied to wool and tested as in Example 3. The results are in Table 31.
• reaction mixture was cooled, further diluted with toluene, washed several times with water to remove the acid catalyst, and dried with anhydrous sodium sulphate. The solvent and other low molecular weight impurities were then removed under reduced pressure, yielding a colourless, viscous polymer in 97% yield.
• a stock emulsion was prepared using 50 grams of polymer, 25 grams of a 50% aqueous solution of a polyoxyethylene alkylphenol surfactant (Lissapol N - I.C.I.), and 175 grams of water. This 20% solids emulsion was used to prepare working strength baths for the application of the polymer to the desired substrate. In cases where the pH of the bath was 8 or above, a clear solution with a purple tinge resulted.
• a polyoxyethylene alkylphenol surfactant Lisapol N - I.C.I.
• Table 32 describes a range of polymers prepared by the method described above, the molar ratio of Polymeg 1000 to 2-mercaptosuccinic acid being varied through the series.
• Polymers XXXIV to XLIV were soluble in aqueous baths of pH 10 and were applied to wool fabric from such baths. They could be cured by heating at 100° C. for 10 minutes in a forced-air oven.
• Table 33 are given the results of tests on fabrics applied by padding at 100% uptake with polymer solutions containing 2% Na 2 CO 3 , drying and after washing. The washes were conducted in 15 liters of pH 7 buffer (Cubex machine).
• Table 36 shows the extra linear shrinkage on washing brought about by exposure to light to blue Standards 6 and 7 and represents the difference between the shrinkage of an irradiated and washed sample and that of a washed unirradiated sample.
• the polymers were applied by padding from an aqueous solution containing 2% Na 2 CO 3 , drying at 100° C., washing and autoclaving. The wash tests were carried out in 15 liters of pH 7 buffer (Cubex machine).
• Table 37 describes polymers prepared by the method of Example 28, using 2-mercaptosuccinic acid and various glycols. It was found that no washing was required if the polymer was not to be subsequently emulsified, and this simplified the process.
• the yield of colourless polymer was 170.3 grams (98% of theory). This polymer was insoluble in pH 10 aqueous baths, but could be applied as an emulsion at pH 10 and cured at 120° C./10 minutes. The results are given in Table 38.
• the colourless, viscous polymer obtained was insoluble in pH 10 aqueous baths, but could be applied from an emulsion at pH 10, and could be cured by heating the fabric at 120° C. for 10 minutes.
• Table 38 gives the results of shrinkage tests, upon washing in 15 liters pH 7 buffer (Cubex machine).
• the polymers in this case were applied by padding with 2% Na 2 CO 3 (on weight of fabric), drying and afterwashing.
• Table 39 gives the results of light fastness tests of polymers XXVII and XLVIII (using a branched chain polyoxypropylene diol) and of polymers XXXIII and XL using unbranched polyoxybutylene chains. 3% polymer by weight of the fabric was applied. It can be seen that the polymers according to the invention are very much more stable to exposure to light.
• Table 40 shows the effect of different washing conditions on fabrics treated with Polymers XXXIX and XLVI.
• the polymers were applied by padding to apply 2% polymer with 2% Na 2 CO 3 on the weight of fabric, drying at 100° C. and afterwashing. Test washing was performed in 15 liters pH 7 buffer (Cubex machine) for the times indicated.
• Table 41 shows the smooth drying index of grey serge treated with Polymers XXXVIII, XL and LI after test washes in 15 liters pH 7 buffer (Cubex machine).
• the polymer-treated samples were prepared by padding together with 2% Na 2 CO 3 (on weight of fabric), drying at 100° C., washing and autoclaving.
• Fabric (doctor flannel and serge) was treated with 2% Polymer XL as described in Example 28, but cured as set out in Table 42. The fabric so cured was left overnight, then washed off, dried, flat-set and wash tested, the results appearing in Table 42.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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• 1973
  • 1973-07-27 GB GB35882/73A patent/GB1480213A/en not_active Expired
• 1974
  • 1974-07-17 IE IE1514/74A patent/IE39622B1/xx unknown
  • 1974-07-19 CA CA205,215A patent/CA1053255A/en not_active Expired
  • 1974-07-22 US US05/490,669 patent/US4032565A/en not_active Expired - Lifetime
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  • 1974-07-26 DE DE2436035A patent/DE2436035C2/de not_active Expired
  • 1974-07-26 FR FR7426124A patent/FR2238728B1/fr not_active Expired
  • 1974-07-26 BR BR6198/74A patent/BR7406198D0/pt unknown
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  • 1974-07-27 JP JP49086527A patent/JPS50100400A/ja active Pending
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